Silicon feedstock for solar cells

ABSTRACT

The present invention relates to silicon feedstock for producing directionally solidified silicon ingots, thin sheets and ribbons for the production of silicon wafers for PV solar cells where the silicon feedstock contains between 0.2 and 10 ppma boron and between 0.1 and 10 ppma phosphorus distributed in the material. The invention further relates to directionally solidified silicon ingot or thin silicon sheet or ribbon for making wafers for solar cells containing between 0.2 ppma and 10 ppma boron and between 0.1 ppma and 10 ppma phosphorus distributed in the ingot, said silicon ingot having a type change from p-type to n-type or from n-type to p-type at a position between 40 and 99% of the ingot height or sheet or ribbon thickness and having a resistivity profile described by an exponential curve having a starting value between 0.4 and 10 ohm cm and where the resistivity value increases towards the type change point. Finally the invention relates to a method for producing silicon feedstock for producing directionally solidified silicon ingots, thin sheets and ribbons for the production of silicon wafers for PV solar cells.

TECHNICAL FIELD

The present invention relates to silicon feedstock for wafers for solarcells, wafers for solar cells, solar cells and a method for theproduction of silicon feedstock for the production of wafers for solarcells.

BACKGROUND TECHNOLOGY

In recent years, photovoltaic solar cells have been produced from ultrapure virgin electronic grade polysilicon (EG-Si) supplemented bysuitable scraps, cuttings and rejects from the electronic chip industry.As a result of the recent downturn experienced by the electronicsindustry, idle polysilicon production capacity has been adapted to makeavailable lower cost grades suitable for manufacturing PV solar cells.This has brought a temporary relief to an otherwise strained market forsolar grade silicon feedstock (SoG-Si) qualities. With demand forelectronic devices returning to normal levels, a major share of thepolysilicon production capacity is expected to be allocated back tosupply the electronics industry, leaving the PV industry short ofsupply. The lack of a dedicated, low cost source of SoG-Si and theresulting supply gap developing is today considered one of the mostserious barriers to further growth of the PV industry.

In recent years, several attempts have been made to develop new sourcesfor SoG-Si that are independent of the electronics industry value chain.Efforts encompass the introduction of new technology to the currentpolysilicon process routes to significantly reduce cost as well as thedevelopment of metallurgical refining processes purifying abundantlyavailable metallurgical grade silicon (MG-Si) to the necessary degree ofpurity. None have so far succeeded in significantly reducing cost ofproduction while providing a silicon feedstock purity expected to berequired to match the performance of PV solar cells produced fromconventional silicon feedstock qualities today.

When producing PV solar cells, a charge of SoG-Si feedstock is prepared,melted and directionally solidified into a square ingot in a specialisedcasting furnace. Before melting, the charge containing SoG-Si feedstockis doped with either boron or phosphorus to produce p-type or n-typeingots respectively. With few exceptions, commercial solar cellsproduced today are based on p-type silicon ingot material. The additionof the single dopant (eg. boron or phosphorus) is controlled to obtain apreferred electrical resistivity in the material, for example in therange between 0.5-1.5 ohm cm. This corresponds to an addition of0.02-0.2 ppma of boron when a p-type ingot is desired and an intrinsicquality (practically pure silicon with negligible content of dopants)SoG-Si feedstock is used. The doping procedure assumes that the contentof the other dopant (in this example case phosphorus) is negligible(P<1/10 B).

If a single doped SoG-Si feedstock of a given resistivity is used invarious addition levels the charge, the addition of dopant is adjustedto take into account the amount of dopant already contained in thepre-doped feedstock material.

Singel doped feedstock qualities of n- and p-type can also be mixed inthe charge to obtain a so-called “compensated” ingot. The type andresistivity of each component of the charge mix must be known to obtaindesired ingot properties.

After casting, the solidified ingot is cut into blocks with thefootprint of the resulting solar cells for example with a surface areaof 125 mm×125 mm). The blocks are sliced into wafers deployingcommercial multi-wire saw equipment.

PV solar cells are produced from the wafers in a number of process stepsof which the most important are surface etching, POCl₃ emitterdiffusion, PECVD SiN deposition, edge isolation and the formation offront and back contacts.

DESCRIPTION OF INVENTION

By the present invention it has now been found that PV solar cellsmeeting commercial efficiency targets can be produced from a SoG-Sifeedstock produced from metallurgical grade silicon by means ofmetallurgical refining processes specifically designed for the PV solarfeedstock application.

Thus according to a first aspect, the present invention relates tosilicon feedstock for producing directionally solidified Czochralski,float zone or multicrystalline silicon ingots, thin silicon sheets orribbons for the production of silicon wafers for PV solar cells, wherethe silicon feedstock is characterised in that it contains between 0.2and 10 ppma boron and between 0.1 and 10 ppma phosphorus distributed inthe material.

According to a preferred embodiment the silicon feedstock containsbetween 0.3 and 5.0 ppma boron and between 0.5 and 3.5 ppma phosphorus.

According to another preferred embodiment, the silicon feedstock(SoG-Si) comprises less than 150 ppma of metallic elements andpreferably less than 50 ppma metallic elements.

According to yet a preferred embodiment the silicon feedstock containsless than 150 ppma carbon and more preferably less than 100 ppma carbon.

The silicon feedstock of the present invention differs substantiallyfrom a charge mix composed of various boron or phosphorus containingsilicon feedstock qualities as described above in that it containshigher levels of both boron and phosphorus. It has surprisingly beenfound that the silicon feedstock of the present invention can be used toproduce solar cells having an efficiency as good as commercial solarcells produced from electronic grade silicon.

The silicon feedstock of the present invention can be used to producedirectionally solidified Czochralski, float zone or multicrystallinesilicon ingots or thin silicon sheet or ribbon for making wafers forsolar cells having high efficiency. Silicon ingots, thin sheets orribbons produced from the silicon feedstock will contain between 0.2ppma and 10 ppma boron and between 0.1 ppma and 10 ppma phosphorus, andwill have a characteristic type change from p-type to n-type or fromn-type to p-type at a position between 40 and 99% of the ingot height orsheet or ribbon thickness. The resisitivity profile of directionallysolidified ingots produced from the feedstock of the present inventionis described by a curve having a starting value between 0.4 and 10 ohmcm where the resistivity value increases towards the type change point.

According to a second aspect, the present invention relates to adirectionally solidified Czochralski, float zone or multicrystallinesilicon ingot or thin silicon sheet or ribbon for making wafers forsolar cells, wherein the silicon ingot, thin sheet or ribbon containsbetween 0.2 ppma and 10 ppma boron and between 0.1 ppma and 10 ppmaphosphorus said silicon ingot having a type change from p-type to n-typeor from n-type to p-type at a position between 40 and 99% of the ingotheight or sheet or ribbon thickness and having a resistivity profiledescribed by a curve having a starting value between 0.4 and 10 ohm cmand where the resistivity value increases towards the type change point.

According to a preferred embodiment the silicon ingot, thin sheet orribbon has a resistivity starting value of between 0.7 and 3 ohm cm.

According to a third aspect, the present invention relates to a methodfor the production of silicon feedstock for producing directionallysolidified Czrochralski, float zone or multicrystalline silicon ingots,thin silicon sheets or ribbons for the production of silicon wafers forPV solar cells which method is characterized in that metallurgical gradesilicon produced in an electric arc furnace by carbothermic reductionfurnace and containing up to 300 ppma boron and up to 100 ppmaphosphorus is subjected to the following refining steps:

-   a) treatment of the metallurgical grade silicon with a    calcium-silicate slag to reduce the boron content of the silicon to    between 0.2 ppma and 10 ppma;-   b) solidifying the slag treated silicon from step a);-   c) leaching the silicon from step b) in at least one leaching step    by an acid leach solution to remove impurities;-   d) melting the silicon from step c);-   e) solidifying the molten silicon from step d) in the form of an    ingot by directional solidification;-   f) removing the upper part of the solidified ingot from step e) to    provide a silicon ingot containing 0.2 to 10 ppma boron and 0.1 to    10 ppma phosphorus;-   g) crushing and/or sizing the silicon from step f).

It has been found that the silicon feedstock produced according to thismethod is well suited for the production of directionally solidifiedingots, thin sheets and ribbons for the production of wafers for solarcells having an efficiency comparable to commercial solar cells.

SHORT DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the resistivity as a function of ingotheight for a first silicon ingot according to the invention, and,

FIG. 2 is a diagram showing the resistivty as a function of ingot heightfor a second silicon ingot according to the invention.

DETAILED DESCRIPTION OF INVENTION EXAMPLE 1

Production of Silicon Feedstock

Commercial metallurgical grade silicon produced by carbothermicreduction in electric arc furnace was treated with a calcium silicateslag to remove mainly boron. Boron was extracted from the molten siliconto the slag phase. The silicon was solidified with very pure siliconcrystals while impurities stayed in the melt until most of the siliconwas solidified. Impurities ended up on the grain boundaries in thesolidified silicon.

The solidified silicon was subjected to acid leaching whereby theintergranular phases was attacked and dissolved together with theimpurities. The remaining undissolved granular silicon was melted andfurther refined to adjust the composition before crusting an sieving toobtain the silicon feedstock for solar grade silicon.

By the method above, two charges of silicon feedstock were produced. Theboron and phosphorus content of the two samples of silicon feedstock areshown in Table 1. TABLE 1 Sample No. ppma boron ppma phosphorus. 1 3.33.2 2 1.2 1.1

EXAMPLE 2

Production of Directionally Solidified Silicon Ingot, Wafers and SolarCells

Silicon feedstock produced according to the method described in Example1 was used to produce two directionally solidified silicon ingotsaccording to the invention. Commercial multicrystalline Si-wafers wereused as reference. A Crystalox DS250 furnace was used for producing theingot. A circular quartz crucible with an inner diameter of 25.5 cm and20 cm height capable of containing about 12 kg of feedstock was used.The grown ingots were squared to 100 cm² and 156 cm² blocks, and thensliced into wafers by a saw. From these blocks, a large number of waferswith thickness in the range of 300-330 μm were produced for cellprocessing.

The content of boron and phosphorus at 20% height of the two ingots areshown in Table 2. TABLE 2 Chemical analysis for ingot # 1 and 2 at 20%of the height. Ingot No. ppma boron ppma phosphorus. 1 2.8 1.3 2 1.0 0.3

The bulk resistivity of the as cut wafers was measured through allblocks by four-point probe on at least each fifth wafer from bottom totop. The bulk resistivity profile of ingot No 1 and 2 is shown in FIG.1, and FIG. 2 respectively. FIGS. 1 and 2 show that the resistivity issubstantially constant from the bottom of the ingot and up to about ¾ ofthe height of the ingot when the material changes from p-type to n-type.

The type of majority carriers in the silicon block was determined byqualitative Seebeck coefficient measurement. Hall-and resistivitymeasurements using van der Paw geometry were applied to obtainresistivity, carrier concentration and mobility on selected wafers fromtop, middle and bottom of each ingot.

All wafers were etched by NaOH for 9 minutes at 80° for saw damageremoval, followed by flushing in deionized water, HCl, deionized waterand 2% HF.

In order to study the effect of light trapping, isotexturisation wasapplied instead of NaOH etching on selected as-cut wafers. This methodcombines the removal of the surface saw damage on the as cut wafer andapplies a surface texturisation in one step.

Solar cells were fabricated by POCl₃ emitter diffusion, PECVD SiNdeposition, and edge isolation by plasma etching. The front and backcontacts are made by screen printing and then firing through.

The efficiency of the fabricated solar cells are shown in Table 3.Efficiencies up to η=14.8% (ingot #2) were reached, which exceed theefficiency values of the reference material. Commercial monocrystallineSi wafers were used as reference for comparison. TABLE 3 Ingot AreaEfficency best cell # [cm²] [%] 1 156 14.3 2 156 14.8 Com Ref 156 14.6

The result from Table 3 shows that solar cells having a efficiencycomparable to and even higher than commercial solar cells can beobtained by the silicon feedstock and the directionally silidifiedsilicon ingots according to the present invention.

1. Silicon feedstock for producing directionally solidified Czochralski,float zone or multicrystalline silicon ingots, thin sheets and ribbonsfor the production of silicon wafers for PV solar cells, characterizedin that the silicon feedstock contains between 0.2 and 10 ppma boron andbetween 0.1 and 10 ppma phosphorus distributed in the material. 2.Silicon feedstock according to claim 1, characterized in that thesilicon feedstock contains between 0.3 and 5.0 ppma boron and between0.5 and 3.5 ppma phosphorus.
 3. Silicon feedstock according to claim 1characterized in that the silicon feedstock comprises less than 150 ppmaof metallic elements.
 4. Silicon feedstock according to claim 3,characterized in that the silicon feedstock comprises less than 50 ppmaof metallic elements.
 5. Silicon feedstock according to claim 1,characterized in that the silicon feedstock contains less than 150 ppmacarbon.
 6. Silicon feedstock according to claim 1, characterized in thatthe silicon feedstock contains less than 100 ppma carbon. 7.Directionally solidified Czochralski, float zone or multicrystallinesilicon ingot or thin silicon sheet or ribbon for making wafers forsolar cells, characterized in that the silicon ingot, thin sheet orribbon contains between 0.2 ppma and 10 ppma boron and between 0.1 ppmaand 10 ppma phosphorus distributed in the ingot, said silicon ingothaving a type change from p-type to n-type or from n-type to p-type at aposition between 40 and 99% of the ingot height or sheet or ribbonthickness and having a resistivity profile described by a curve having astarting value between 0.4 and 10 ohm cm and where the resistivity valueincreases towards the type change point.
 8. Directional solidifiedsilicon ingot, thin sheet or ribbon according to claim 7, characterizedin that resistivity starting value is between 0.7 and 3 ohm cm. 9.Method for the production of silicon feedstock for producingdirectionally solidified Czochralski, float zone or multicrystallinesilicon ingots, thin silicon sheets or ribbons for the production ofsilicon wafers for PV solar cells, characterized in that metallurgicalgrade silicon produced in an electric arc furnace by carbothermicreduction furnace and containing up to 300 ppma boron and up to 100 ppmaphosphorus is subjected to the following refining steps: a) treatment ofthe metallurgical grade silicon with a calcium-silicate slag to reducethe boron content of the silicon to between 0.2 and 10 ppma; b)solidifying the slag treated silicon from the step a); c) leaching thesilicon from step b) in at least one leaching step by an acid leachsolution to remove impurities; d) melting the silicon from step c); e)solidifying the molten silicon from step d) in the form of an ingot bydirectional solidification; f) removing the upper part of the solidifiedingot from step e) to provide a silicon ingot containing 0.2 to 10 ppmaboron and 0.1 to 10 ppma phosphorus; g) crushing and/or sizing thesilicon from step f).